CA2729044C - Lid for closing a cup - Google Patents
Lid for closing a cup Download PDFInfo
- Publication number
- CA2729044C CA2729044C CA2729044A CA2729044A CA2729044C CA 2729044 C CA2729044 C CA 2729044C CA 2729044 A CA2729044 A CA 2729044A CA 2729044 A CA2729044 A CA 2729044A CA 2729044 C CA2729044 C CA 2729044C
- Authority
- CA
- Canada
- Prior art keywords
- lid
- layer
- sealing rim
- line
- polymer film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000007789 sealing Methods 0.000 claims abstract description 109
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 84
- -1 polyethylene Polymers 0.000 claims abstract description 74
- 239000004743 Polypropylene Substances 0.000 claims abstract description 72
- 229920001155 polypropylene Polymers 0.000 claims abstract description 71
- 239000004698 Polyethylene Substances 0.000 claims abstract description 60
- 229920000573 polyethylene Polymers 0.000 claims abstract description 60
- 229920003023 plastic Polymers 0.000 claims abstract description 20
- 239000004033 plastic Substances 0.000 claims abstract description 20
- 239000010410 layer Substances 0.000 claims description 140
- 229920006254 polymer film Polymers 0.000 claims description 69
- 239000011888 foil Substances 0.000 claims description 67
- 239000002346 layers by function Substances 0.000 claims description 58
- 229920000642 polymer Polymers 0.000 claims description 47
- 239000000463 material Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 33
- 239000003814 drug Substances 0.000 claims description 20
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 19
- 238000009472 formulation Methods 0.000 claims description 18
- 239000007767 bonding agent Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 10
- 239000002966 varnish Substances 0.000 claims description 9
- 230000003313 weakening effect Effects 0.000 claims description 9
- 239000000454 talc Substances 0.000 claims description 8
- 229910052623 talc Inorganic materials 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 7
- 229920002397 thermoplastic olefin Polymers 0.000 claims description 7
- 229920001519 homopolymer Polymers 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 230000002093 peripheral effect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 8
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 7
- 239000005043 ethylene-methyl acrylate Substances 0.000 description 7
- 230000035622 drinking Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229920003312 Appeel® Polymers 0.000 description 3
- 101100327917 Caenorhabditis elegans chup-1 gene Proteins 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 235000013372 meat Nutrition 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 239000003826 tablet Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 229920003182 Surlyn® Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 235000015218 chewing gum Nutrition 0.000 description 1
- 229940112822 chewing gum Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000013532 laser treatment Methods 0.000 description 1
- 239000007937 lozenge Substances 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 235000010603 pastilles Nutrition 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- KNXVOGGZOFOROK-UHFFFAOYSA-N trimagnesium;dioxido(oxo)silane;hydroxy-oxido-oxosilane Chemical compound [Mg+2].[Mg+2].[Mg+2].O[Si]([O-])=O.O[Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O KNXVOGGZOFOROK-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D77/00—Packages formed by enclosing articles or materials in preformed containers, e.g. boxes, cartons, sacks or bags
- B65D77/10—Container closures formed after filling
- B65D77/20—Container closures formed after filling by applying separate lids or covers, i.e. flexible membrane or foil-like covers
- B65D77/2024—Container closures formed after filling by applying separate lids or covers, i.e. flexible membrane or foil-like covers the cover being welded or adhered to the container
- B65D77/2028—Means for opening the cover other than, or in addition to, a pull tab
- B65D77/2032—Means for opening the cover other than, or in addition to, a pull tab by peeling or tearing the cover from the container
- B65D77/2044—Means for opening the cover other than, or in addition to, a pull tab by peeling or tearing the cover from the container whereby a layer of the container or cover fails, e.g. cohesive failure
- B65D77/2048—Means for opening the cover other than, or in addition to, a pull tab by peeling or tearing the cover from the container whereby a layer of the container or cover fails, e.g. cohesive failure whereby part of the container or cover has been weakened, e.g. perforated or precut
- B65D77/2056—Means for opening the cover other than, or in addition to, a pull tab by peeling or tearing the cover from the container whereby a layer of the container or cover fails, e.g. cohesive failure whereby part of the container or cover has been weakened, e.g. perforated or precut the cover being weakened
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/31—Heat sealable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2435/00—Closures, end caps, stoppers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2581/00—Seals; Sealing equipment; Gaskets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D2577/00—Packages formed by enclosing articles or materials in preformed containers, e.g. boxes, cartons, sacks, bags
- B65D2577/10—Container closures formed after filling
- B65D2577/20—Container closures formed after filling by applying separate lids or covers
- B65D2577/2075—Lines of weakness or apertures
- B65D2577/2091—Lines of weakness or apertures in cover
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31692—Next to addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
Abstract
The invention relates to a lid (2) for closing a cup (1) along a peripheral sealing edge (10). Said lid comprises at least one aluminum film and an optionally multi-layered plastic layer which is co-extruded onto the aluminum film and has a closed predetermined tearing line (3). The invention is characterized in that the plastic layer is made of plastic based on polyethylene (PE) or plastic based on polypropylene (PP) and that the predetermined tearing line is introduced into the plastic layer preferably by means of a CO2 laser. In one embodiment, said predetermined tearing line (3) is provided directly in the region of the sealing edge (10). The invention also relates to a method for producing such a lid.
Description
¨
Lid for closing a cup The invention relates to a lid for closing a cup along a circumferential sealing rim, where the lid comprises at least one aluminum foil and an optionally multilayer polymer film coextruded on to the aluminum foil and a cohesive line of weakness is provided in the polymer film, corresponding to the preamble of claim 1.
Such a lid is known, for example, from WO 2008/006123 A, corresponding to AT 009 750 U and EP 2 040 915 A, published in 2008. This document concentrates on the structure of the material layers forming the contact surface on the two sides of the contact surface.
It is known from WO 2007/065055 A, corresponding to EP 1 954 582 A and US 4,693,390, published in 2007, that the two layers can be adhesively bonded to one another; the line of weakness is introduced by means of a laser beam which is not described in more detail.
EP 0 812 782 A, published in 1997, likewise discloses such a lid. Here, the polymer film comprises at least two layers, with the innermost layer having incisions or lines of weakness near the rim which bound oval regions. After sealing onto a filled cup, peeling off the lid results, due to the predetermined adhesion conditions between the individual layers and the strength of the seal at the rim of the cup, in the inner layer of the plastic film remaining firmly sealed to the container rim, the outer layer of the plastic film and the aluminum foil being peeled off and the oval region which is defined by the lines of weakness of the innermost film remaining adhering to the outer layer on peeling off and thus providing an opening suitable for a drinking straw or drinking from the cup.
, , =
Lid for closing a cup The invention relates to a lid for closing a cup along a circumferential sealing rim, where the lid comprises at least one aluminum foil and an optionally multilayer polymer film coextruded on to the aluminum foil and a cohesive line of weakness is provided in the polymer film, corresponding to the preamble of claim 1.
Such a lid is known, for example, from WO 2008/006123 A, corresponding to AT 009 750 U and EP 2 040 915 A, published in 2008. This document concentrates on the structure of the material layers forming the contact surface on the two sides of the contact surface.
It is known from WO 2007/065055 A, corresponding to EP 1 954 582 A and US 4,693,390, published in 2007, that the two layers can be adhesively bonded to one another; the line of weakness is introduced by means of a laser beam which is not described in more detail.
EP 0 812 782 A, published in 1997, likewise discloses such a lid. Here, the polymer film comprises at least two layers, with the innermost layer having incisions or lines of weakness near the rim which bound oval regions. After sealing onto a filled cup, peeling off the lid results, due to the predetermined adhesion conditions between the individual layers and the strength of the seal at the rim of the cup, in the inner layer of the plastic film remaining firmly sealed to the container rim, the outer layer of the plastic film and the aluminum foil being peeled off and the oval region which is defined by the lines of weakness of the innermost film remaining adhering to the outer layer on peeling off and thus providing an opening suitable for a drinking straw or drinking from the cup.
, , =
- 2 -The creation of the adhesion between the individual films/layers and the lines of weakness is achieved by means of melting processes which are brought about by means of appropriately heated and profiled rollers while the film runs through them. Although this application originating in the year 1996 comes from one of the largest lid manufacturers in Europe, the subject matter of the patent application never came on to the market; it was not possible to produce it in a commercially justifiable time and at commercially justifiable cost.
EP 1 278 630 B discloses a similar lid which is said to be resealable after opening. For this purpose, a pressure-sensitive adhesive is provided in particular regions of the lids. Apart from the resealability, there are various similarities with the first-named document when the lid is made more mechanically stable in the interests of resealability. For opening only once, this lid is too complicated, and in addition it has been found, in this design, that the separation between the layers is unreliable and the inner layer does not reliably remain in the region of the opening.
AT 501 789 B by the applicant is of an earlier date and has the same objectives as the first-named document and likewise attempts to create the lines of weakness by means of a heatable tool in a thermomechanical way.
Here too, reliable and commercially justifiable production is not successful.
A document from far back in 1979, viz. DE 29 01 581 A, attempted to provide a solution to peeling off a layer of a multilayer lid on specific cups having a rolled rim so as to form an opening in the remaining lid material, but this product never came on to the market either.
, . , ,
EP 1 278 630 B discloses a similar lid which is said to be resealable after opening. For this purpose, a pressure-sensitive adhesive is provided in particular regions of the lids. Apart from the resealability, there are various similarities with the first-named document when the lid is made more mechanically stable in the interests of resealability. For opening only once, this lid is too complicated, and in addition it has been found, in this design, that the separation between the layers is unreliable and the inner layer does not reliably remain in the region of the opening.
AT 501 789 B by the applicant is of an earlier date and has the same objectives as the first-named document and likewise attempts to create the lines of weakness by means of a heatable tool in a thermomechanical way.
Here too, reliable and commercially justifiable production is not successful.
A document from far back in 1979, viz. DE 29 01 581 A, attempted to provide a solution to peeling off a layer of a multilayer lid on specific cups having a rolled rim so as to form an opening in the remaining lid material, but this product never came on to the market either.
, . , ,
- 3 -A similarly old document, viz. FR 2 503 036 A, proposes a very similar solution, namely coextrusion of an aluminum foil and a polymer film, the latter being separated from the composite by lines of weakness in the prescribed regions and being taken off by the aluminum when the lid is peeled off in these places, so that a lid having an opening remains at the rim of the cup even after opening.
Even considerably later (1987), the application of the last-named French document protected an improvement in the USA, but none of the products came on to the market despite the large patenting efforts.
A document concerning somewhat different objectives which goes back to 1971 is DE 22 40 234 A, which seals a two-layer covering film to the container rim in dish-shaped packaging for fresh meat, with the outer layer being impermeable to oxygen and the inner layer being permeable to oxygen. As a result of a weakening of the inner layer in the region of a peeling tab, it is possible to peel off the outer layer alone and thus allow the ageing process for the meat to commence. This packaging was not able to become established, if it appeared on the market at all.
A recent, once again generic, document is WO 2007/088426 A, which contains a series of variants of the documents discussed above (in particular the first-named document). It is notable here that the treatises are extremely cursory so that they actually put forward only ideas but not actually functional solutions. This can be seen in a comparison of fig. 4 with the associated description, since fig. 4 is supposed to represent the case in which the outer side of the lid has the lines of weakness, but this means that the hatched part having the reference numeral 24 cannot assume the position shown on being peeled off,
Even considerably later (1987), the application of the last-named French document protected an improvement in the USA, but none of the products came on to the market despite the large patenting efforts.
A document concerning somewhat different objectives which goes back to 1971 is DE 22 40 234 A, which seals a two-layer covering film to the container rim in dish-shaped packaging for fresh meat, with the outer layer being impermeable to oxygen and the inner layer being permeable to oxygen. As a result of a weakening of the inner layer in the region of a peeling tab, it is possible to peel off the outer layer alone and thus allow the ageing process for the meat to commence. This packaging was not able to become established, if it appeared on the market at all.
A recent, once again generic, document is WO 2007/088426 A, which contains a series of variants of the documents discussed above (in particular the first-named document). It is notable here that the treatises are extremely cursory so that they actually put forward only ideas but not actually functional solutions. This can be seen in a comparison of fig. 4 with the associated description, since fig. 4 is supposed to represent the case in which the outer side of the lid has the lines of weakness, but this means that the hatched part having the reference numeral 24 cannot assume the position shown on being peeled off,
- 4 -because it is the outermost layer which is separated off.
It is stated elsewhere in the text that the lines of weakness can also be provided on the innermost layer or, when more than two films/layers are present, also at the intermediate layers. How this is supposed to function either in production or on opening is not indicated in more detail.
For the production of the lines of weakness, too, mention is merely made of all conceivable possibilities without even one of these being described in detail. It is merely said quite succinctly that a stamping tool or the like or a laser beam can be used. This document is, as mentioned above, of relatively recent date (priority February 2, 2006) and no product corresponding to the content of this document has yet appeared on the market; it would hardly be possible to manufacture such a product on an industrial scale on the basis of the information given in the patent application.
Conventional lids which are sealed to a cup along a circumferential sealing rim for full-area opening suffer from problems that the sealing strengths actually achieved are time and time again too great for normal opening and tearing of the lid, spillage of the contents of the cup because of the great amount of force which has to be applied and similar unpleasant effects therefore occur. The reason is that the packaging companies at which sealing is carried out pay attention mainly to the seal being impermeable and, in the event of problems which are sometimes attributable to a dirty tool, poorly aligned lid feed, etc., tend simply to alter the parameters for the sealing strength (temperature, pressure, time) on the sealing machine so that the desired impermeability of the seal is obtained in each case. However, this virtually inevitably leads
It is stated elsewhere in the text that the lines of weakness can also be provided on the innermost layer or, when more than two films/layers are present, also at the intermediate layers. How this is supposed to function either in production or on opening is not indicated in more detail.
For the production of the lines of weakness, too, mention is merely made of all conceivable possibilities without even one of these being described in detail. It is merely said quite succinctly that a stamping tool or the like or a laser beam can be used. This document is, as mentioned above, of relatively recent date (priority February 2, 2006) and no product corresponding to the content of this document has yet appeared on the market; it would hardly be possible to manufacture such a product on an industrial scale on the basis of the information given in the patent application.
Conventional lids which are sealed to a cup along a circumferential sealing rim for full-area opening suffer from problems that the sealing strengths actually achieved are time and time again too great for normal opening and tearing of the lid, spillage of the contents of the cup because of the great amount of force which has to be applied and similar unpleasant effects therefore occur. The reason is that the packaging companies at which sealing is carried out pay attention mainly to the seal being impermeable and, in the event of problems which are sometimes attributable to a dirty tool, poorly aligned lid feed, etc., tend simply to alter the parameters for the sealing strength (temperature, pressure, time) on the sealing machine so that the desired impermeability of the seal is obtained in each case. However, this virtually inevitably leads
- 5 -to the abovementioned overstrong bonding regions being created at individual places along the sealing seam, which present the user with the abovementioned unacceptable problems. Some embodiments of the present disclosure are directed to this problem.
The applicant has been intensively concerned with the abovementioned problems and the attempted solutions in the documents mentioned and has now found a practicable solution, which, in some embodiments, the desired objectives may be achieved and the disadvantages indicated may be avoided.
According to an aspect of the present invention, there is provided a lid for closing a cup along a circumferential sealing rim, the lid comprising at least an aluminum foil and a plastics material film coextruded onto the aluminum foil, a cohesive line of weakness being provided in the plastics material film, at least one layer of the plastics material film comprising either polyethylene (PE)-based plastics material or polypropylene (PP)-based plastics material, wherein the aluminum layer is adjoined by a layer based on ethylene-acrylic acid copolymers and at least one functional layer attached thereto, which contains mainly polyethylene and polypropylene polymers.
According to another aspect of the present invention, there is provided a lid for closing a cup along a circumferential sealing rim, the lid comprising: an aluminum foil; and a functional layer coextruded onto the aluminum foil; wherein the functional layer comprises one or more layers of a polymer film that is based upon polyethylene (PE), polypropylene (PP), or a mixture thereof; the polymer film including a cohesive line of weakness introduced by means of a 002 laser; wherein the aluminum foil is adjoined to the polymer film by a bonding agent that includes ethylene-acrylic acid copolymers.
- 5a -According to another aspect of the present invention, there is provided a sealed cup, wherein the cup has a circumferential sealing rim and a lid forming a seal along the circumferential sealing rim, the lid comprising: an outer aluminum foil layer;
and a functional layer coextruded onto the aluminum foil layer;
wherein the functional layer has a thickness of about 70 pm and includes three layers of polymer film based on polyethylene, wherein the layer facing the cup interior includes an unfilled polyethylene polymer formulation in an amount of 14 g/m2, the middle layer includes a polyethylene polymer formulation including talc filler in an amount of 49 g/m2, and the layer facing the aluminum foil includes the unfilled polyethylene polymer formulation in an amount of 7 g/m2; wherein the functional layer is joined to the aluminum foil layer by a bonding agent that includes ethylene-acrylic acid copolymers; and the functional layer includes a cohesive line of weakness in one or more constituent polymer films introduced by means of a CO2 laser, the cohesive line of weakness disposed in a region of the functional layer adjacent to the circumferential sealing rim, the region being bounded by an inner line that is disposed not more than twice the width of the sealing rim from an inner contour of the sealing rim in an inward direction, and an outer line that is disposed a maximum of one-third of the width of the sealing rim outside an inner contour of the sealing rim.
According to another aspect of the present invention, there is provided a sealed cup, wherein the cup has a circumferential sealing rim and a lid forming a seal along the circumferential sealing rim, the lid comprising: an outer aluminum foil layer;
and a functional layer coextruded onto the aluminum foil layer;
wherein the functional layer has a thickness of about 70 pm and includes three layers of polymer film based on polypropylene, - 5b -wherein the layer facing the cup interior includes an unfilled polypropylene polymer formulation in an amount of 16 g/m2, the middle layer includes a filled polypropylene polymer formulation in an amount of 28 g/m2 and the layer facing the aluminum foil includes the unfilled polypropylene polymer formulation in an amount of 6 g/m2; wherein the functional layer is joined to the aluminum foil layer by a bonding agent that includes ethylene-acrylic acid copolymers; and the functional layer includes a cohesive line of weakness in one or more constituent polymer films introduced by means of a CO2 laser, the cohesive line of weakness disposed in a region of the functional layer adjacent to the circumferential sealing rim, the region being bounded by an inner line that is disposed not more than twice the width of the sealing rim from an inner contour of the sealing rim in an inward direction, and an outer line that is disposed a maximum of one-third of the width of the sealing rim outside an inner contour of the sealing rim.
According to another aspect of the present invention, there is provided a process for producing a lid for closing a cup along a circumferential sealing rim, where the lid comprises at least one aluminum foil and a polymer film coextruded on to the aluminum foil and a cohesive line of weakness is provided in the polymer film, where at least one layer of the polymer film comprises either polymer based on polyethylene (PE) or polymer based on polypropylene (PP) and where the line of weakness has been introduced into the polymer film by means of a laser, wherein lid material in the form of a continuous sheet is conveyed, with the polymer film facing the laser and sliding on an appropriate support, past the laser and the laser beam is focused to a diameter of from 150 pm to 350 pm, and the beam is focused on to a point above the aluminum foil.
- 5c -According to another aspect of the present invention, there is provided a medicine bottle which is closed by a lid along a circumferential sealing rim, where the lid comprises at least one aluminum foil and a polymer film coextruded on to the aluminum foil and a cohesive line of weakness is provided in the polymer film, wherein at least one layer of the polymer film comprises either polymer based on polyethylene (PE) or polymer based on polypropylene (PP) and the line of weakness has been introduced into the polymer film by means of a CO2 laser.
One aspect of the present invention includes an optionally multilayer, polymer film comprising either polymer based on polyethylene (PE) or polymer based on polypropylene (PP) and lines of weakness preferably being introduced into the polymer film by means of a CO2 laser.
This gives a weakening of the polymer film which is restricted to very small areas or a very small volume and whose properties, according to present-day knowledge, can be attributed to the as good as exclusively thermal stressing of the polymer material, as a result of which the regions bounded by the line of weakness reliably remain adhering to the aluminum foil on peeling off and a cleanly delineated removal opening or drinking opening is formed by the polymer film which remains sealed on to the rim of the cup.
The small dimensions of the weakened regions and the weakening by means of heat alone without pressure or shear stress, thus at least essentially without mechanical material deformation, also lead to the material present in the cup not coming into contact with the aluminum layer despite the lines of weakness. This is particularly important in the case of foods having an appreciable proportion of fruit acids since
The applicant has been intensively concerned with the abovementioned problems and the attempted solutions in the documents mentioned and has now found a practicable solution, which, in some embodiments, the desired objectives may be achieved and the disadvantages indicated may be avoided.
According to an aspect of the present invention, there is provided a lid for closing a cup along a circumferential sealing rim, the lid comprising at least an aluminum foil and a plastics material film coextruded onto the aluminum foil, a cohesive line of weakness being provided in the plastics material film, at least one layer of the plastics material film comprising either polyethylene (PE)-based plastics material or polypropylene (PP)-based plastics material, wherein the aluminum layer is adjoined by a layer based on ethylene-acrylic acid copolymers and at least one functional layer attached thereto, which contains mainly polyethylene and polypropylene polymers.
According to another aspect of the present invention, there is provided a lid for closing a cup along a circumferential sealing rim, the lid comprising: an aluminum foil; and a functional layer coextruded onto the aluminum foil; wherein the functional layer comprises one or more layers of a polymer film that is based upon polyethylene (PE), polypropylene (PP), or a mixture thereof; the polymer film including a cohesive line of weakness introduced by means of a 002 laser; wherein the aluminum foil is adjoined to the polymer film by a bonding agent that includes ethylene-acrylic acid copolymers.
- 5a -According to another aspect of the present invention, there is provided a sealed cup, wherein the cup has a circumferential sealing rim and a lid forming a seal along the circumferential sealing rim, the lid comprising: an outer aluminum foil layer;
and a functional layer coextruded onto the aluminum foil layer;
wherein the functional layer has a thickness of about 70 pm and includes three layers of polymer film based on polyethylene, wherein the layer facing the cup interior includes an unfilled polyethylene polymer formulation in an amount of 14 g/m2, the middle layer includes a polyethylene polymer formulation including talc filler in an amount of 49 g/m2, and the layer facing the aluminum foil includes the unfilled polyethylene polymer formulation in an amount of 7 g/m2; wherein the functional layer is joined to the aluminum foil layer by a bonding agent that includes ethylene-acrylic acid copolymers; and the functional layer includes a cohesive line of weakness in one or more constituent polymer films introduced by means of a CO2 laser, the cohesive line of weakness disposed in a region of the functional layer adjacent to the circumferential sealing rim, the region being bounded by an inner line that is disposed not more than twice the width of the sealing rim from an inner contour of the sealing rim in an inward direction, and an outer line that is disposed a maximum of one-third of the width of the sealing rim outside an inner contour of the sealing rim.
According to another aspect of the present invention, there is provided a sealed cup, wherein the cup has a circumferential sealing rim and a lid forming a seal along the circumferential sealing rim, the lid comprising: an outer aluminum foil layer;
and a functional layer coextruded onto the aluminum foil layer;
wherein the functional layer has a thickness of about 70 pm and includes three layers of polymer film based on polypropylene, - 5b -wherein the layer facing the cup interior includes an unfilled polypropylene polymer formulation in an amount of 16 g/m2, the middle layer includes a filled polypropylene polymer formulation in an amount of 28 g/m2 and the layer facing the aluminum foil includes the unfilled polypropylene polymer formulation in an amount of 6 g/m2; wherein the functional layer is joined to the aluminum foil layer by a bonding agent that includes ethylene-acrylic acid copolymers; and the functional layer includes a cohesive line of weakness in one or more constituent polymer films introduced by means of a CO2 laser, the cohesive line of weakness disposed in a region of the functional layer adjacent to the circumferential sealing rim, the region being bounded by an inner line that is disposed not more than twice the width of the sealing rim from an inner contour of the sealing rim in an inward direction, and an outer line that is disposed a maximum of one-third of the width of the sealing rim outside an inner contour of the sealing rim.
According to another aspect of the present invention, there is provided a process for producing a lid for closing a cup along a circumferential sealing rim, where the lid comprises at least one aluminum foil and a polymer film coextruded on to the aluminum foil and a cohesive line of weakness is provided in the polymer film, where at least one layer of the polymer film comprises either polymer based on polyethylene (PE) or polymer based on polypropylene (PP) and where the line of weakness has been introduced into the polymer film by means of a laser, wherein lid material in the form of a continuous sheet is conveyed, with the polymer film facing the laser and sliding on an appropriate support, past the laser and the laser beam is focused to a diameter of from 150 pm to 350 pm, and the beam is focused on to a point above the aluminum foil.
- 5c -According to another aspect of the present invention, there is provided a medicine bottle which is closed by a lid along a circumferential sealing rim, where the lid comprises at least one aluminum foil and a polymer film coextruded on to the aluminum foil and a cohesive line of weakness is provided in the polymer film, wherein at least one layer of the polymer film comprises either polymer based on polyethylene (PE) or polymer based on polypropylene (PP) and the line of weakness has been introduced into the polymer film by means of a CO2 laser.
One aspect of the present invention includes an optionally multilayer, polymer film comprising either polymer based on polyethylene (PE) or polymer based on polypropylene (PP) and lines of weakness preferably being introduced into the polymer film by means of a CO2 laser.
This gives a weakening of the polymer film which is restricted to very small areas or a very small volume and whose properties, according to present-day knowledge, can be attributed to the as good as exclusively thermal stressing of the polymer material, as a result of which the regions bounded by the line of weakness reliably remain adhering to the aluminum foil on peeling off and a cleanly delineated removal opening or drinking opening is formed by the polymer film which remains sealed on to the rim of the cup.
The small dimensions of the weakened regions and the weakening by means of heat alone without pressure or shear stress, thus at least essentially without mechanical material deformation, also lead to the material present in the cup not coming into contact with the aluminum layer despite the lines of weakness. This is particularly important in the case of foods having an appreciable proportion of fruit acids since
- 6 -these could lead to local discoloration of the aluminum, which is undesirable for reasons of appearance.
The individual constituents of the lid and the operations during laser treatment are described in detail below.
The aluminum foil can comprise the aluminum alloys usual for lids or aluminum having the usual degree of purity. The surface can be shiny or matte, and the thickness can be, for example, 50 pm, although wide variations are possible here. Preference is given to using a "soft" aluminum foil; to a person skilled in the field of lid manufacture, this is a familiar term and therefore does not need to be discussed in more detail here.
On the outside of the aluminum foil, i.e. the side facing away from the coextruded polymer film, there is usually some printing which is not affected by the configuration according to the invention of the lid and in turn does not affect the invention and can therefore be applied in all ways known in the prior art, usually on a layer of printing primer, and can, for example, be UV flexographic printing. Use of an embossed aluminum foil is also possible.
A layer of heat sealing varnish, usually PVC-free and preferably colorless, can be applied to the side facing the coextruded polymer film in order to bring the thickness of the bond between the aluminum foil and the polymer film to the desired dimension. Usual values for the amounts used are in the region of about 6 g/m2.
This heat sealing varnish layer is not absolutely necessary; a few simple experiments will allow a person skilled in the art to determine whether and in what ,
The individual constituents of the lid and the operations during laser treatment are described in detail below.
The aluminum foil can comprise the aluminum alloys usual for lids or aluminum having the usual degree of purity. The surface can be shiny or matte, and the thickness can be, for example, 50 pm, although wide variations are possible here. Preference is given to using a "soft" aluminum foil; to a person skilled in the field of lid manufacture, this is a familiar term and therefore does not need to be discussed in more detail here.
On the outside of the aluminum foil, i.e. the side facing away from the coextruded polymer film, there is usually some printing which is not affected by the configuration according to the invention of the lid and in turn does not affect the invention and can therefore be applied in all ways known in the prior art, usually on a layer of printing primer, and can, for example, be UV flexographic printing. Use of an embossed aluminum foil is also possible.
A layer of heat sealing varnish, usually PVC-free and preferably colorless, can be applied to the side facing the coextruded polymer film in order to bring the thickness of the bond between the aluminum foil and the polymer film to the desired dimension. Usual values for the amounts used are in the region of about 6 g/m2.
This heat sealing varnish layer is not absolutely necessary; a few simple experiments will allow a person skilled in the art to determine whether and in what ,
- 7 -amount it is required or advantageous in the particular application.
The structure described above is the same for both PE-based and PP-based, coextruded, optionally multilayer, films. Various percentages are indicated below; these are always percentages by weight unless other specific bases are specifically indicated.
When a PE-based coextrudate is used, it can be filled, for example with talc (e.g. CC7209 from Borealis), chalk, TiO2 or other fillers known from the prior art;
it is also possible to use dies which are matched, in particular, to the color of the later filled material.
Filler contents of up to 40% and more are possible. As talc, it is possible to use, for example, Finntalc M05 SL. There are also "prefilled" systems, for example Maxithen HP 790101 from Gabriel Chemie, or Carolen 252550 from Carova Compounding, which can be fed directly into the extruder.
It is of course also possible to use unfilled PE grades when their rheological properties are suitable for processing on the coating apparatus available, in particular a slit die. This can be determined without problems by a person skilled in the field of extrusion technology on the basis of a knowledge of the invention. Suitable MFI values (melt index, for example in accordance with DIN; 190 C, load of 2.16 kg) are in the range from 2 to 10 g/10 min.
Examples of useable products which are available on the market are:
Escorene LD 252 from Exxon;
PG 7004 from Dow: WA 107672/01/014: 50 g;
PG 7008 from Dow;
CA 8200 from Borealis;
Bralen NA 7-25 from Sovnaft Petrochemicals.
The structure described above is the same for both PE-based and PP-based, coextruded, optionally multilayer, films. Various percentages are indicated below; these are always percentages by weight unless other specific bases are specifically indicated.
When a PE-based coextrudate is used, it can be filled, for example with talc (e.g. CC7209 from Borealis), chalk, TiO2 or other fillers known from the prior art;
it is also possible to use dies which are matched, in particular, to the color of the later filled material.
Filler contents of up to 40% and more are possible. As talc, it is possible to use, for example, Finntalc M05 SL. There are also "prefilled" systems, for example Maxithen HP 790101 from Gabriel Chemie, or Carolen 252550 from Carova Compounding, which can be fed directly into the extruder.
It is of course also possible to use unfilled PE grades when their rheological properties are suitable for processing on the coating apparatus available, in particular a slit die. This can be determined without problems by a person skilled in the field of extrusion technology on the basis of a knowledge of the invention. Suitable MFI values (melt index, for example in accordance with DIN; 190 C, load of 2.16 kg) are in the range from 2 to 10 g/10 min.
Examples of useable products which are available on the market are:
Escorene LD 252 from Exxon;
PG 7004 from Dow: WA 107672/01/014: 50 g;
PG 7008 from Dow;
CA 8200 from Borealis;
Bralen NA 7-25 from Sovnaft Petrochemicals.
- 8 -These PE grades (normally LDPE) (LD = low density) can be used in pure form or as a mixture. To increase the stiffness, HDPE (HD = high density) having a similar flow behavior can be added; when tougher mixtures are required, rubber-like types, known as thermoplastic elastomers (EPDM, etc.) can also be added. The addition of polybutylene (for instance 8340 M or DP 9217 from Basell or ethylene copolymers such as EAA (ethylene-acrylic acid copolymer), EMA (ethylene-methacrylate copolymer), or ionomers (based on ethylene-acrylic acid, individual acid groups replaced by ions) in an amount of up to 30% is also possible.
When a PP-based coextrudate is used, it can likewise be filled or unfilled.
Unfilled grades preferably have an MFI of from 8 to 22 g/10 min (melt index, for example in accordance with DIN; 230 C, load of 2.16 kg). Possibilities are PP
homopolymers, PP copolymers, branched PP grades (known as HMS-PP grades), metallocene, heterophase PP grades, and also mixtures in this viscosity range and blends.
To improve the properties, a proportion of PE can be added (e.g. WG 341 C from Borealis, which contains about 30% of PE, or else another polyolefin-based material, e.g. polybutylene). The suitability for processing to produce flat structures in extrusion plants can in the case of doubt easily be determined by a person skilled in the field of plastics extrusion, if appropriate by means of a few experiments on the laboratory scale. Any proportion of PE, as mentioned above, can also be significantly higher than the 30%
mentioned in the case of lids which are not sterilized.
Examples of useable products which are obtainable on the market are:
WG 341C from Borealis;
Daploy WD 234 HMS from Borealis;
,
When a PP-based coextrudate is used, it can likewise be filled or unfilled.
Unfilled grades preferably have an MFI of from 8 to 22 g/10 min (melt index, for example in accordance with DIN; 230 C, load of 2.16 kg). Possibilities are PP
homopolymers, PP copolymers, branched PP grades (known as HMS-PP grades), metallocene, heterophase PP grades, and also mixtures in this viscosity range and blends.
To improve the properties, a proportion of PE can be added (e.g. WG 341 C from Borealis, which contains about 30% of PE, or else another polyolefin-based material, e.g. polybutylene). The suitability for processing to produce flat structures in extrusion plants can in the case of doubt easily be determined by a person skilled in the field of plastics extrusion, if appropriate by means of a few experiments on the laboratory scale. Any proportion of PE, as mentioned above, can also be significantly higher than the 30%
mentioned in the case of lids which are not sterilized.
Examples of useable products which are obtainable on the market are:
WG 341C from Borealis;
Daploy WD 234 HMS from Borealis;
,
- 9 -Hifax DKS 208 nat. from Basell;
Domolen 1011S from Domo.
Example of a mixture:
56% WG3410 with 30% WD 234 HMS and 14% HG 420 FB
(from Borealis).
Filled grades are commercially available, e.g. WG 350C
from Borealis, but can of course also be mixed by the user; a mixture of 80% of WG341 C with 20% of VATPOL
265F65 (with 60% of filler) from SILON has been found to be useful.
As colorants, it is possible to use all conventional colorant masterbatches, e.g. for coffee brown HP 820761 or PP 821361 from Gabriel Chemie, and for white the usual Ti02.
Multilayer structures of the coextrusion layer are possible for both PE-based and PP-based polymers and are in many cases advantageous. Here, in the case of a symmetrical structure, the outer layers can be selected so that they have the best possible properties for discharge of the coextrudate at the slit die and that the inner layer(s) has/have the desired mechanical and/or thermal properties.
Both in this case and especially in the case of an unsymmetrical structure, the outer layer facing away from the aluminum foil (later located on the container side) can also take account of the nature of the material of the cup/container on to the rim of which the lid is sealed. In this case, this may be a layer of Appeel 20D745 from DuPont, optionally with from 2 to 5%
of lubricant additive such as Conpol 20S2 from DuPont, in order to seal both against PS cups and against PP
cups.
,
Domolen 1011S from Domo.
Example of a mixture:
56% WG3410 with 30% WD 234 HMS and 14% HG 420 FB
(from Borealis).
Filled grades are commercially available, e.g. WG 350C
from Borealis, but can of course also be mixed by the user; a mixture of 80% of WG341 C with 20% of VATPOL
265F65 (with 60% of filler) from SILON has been found to be useful.
As colorants, it is possible to use all conventional colorant masterbatches, e.g. for coffee brown HP 820761 or PP 821361 from Gabriel Chemie, and for white the usual Ti02.
Multilayer structures of the coextrusion layer are possible for both PE-based and PP-based polymers and are in many cases advantageous. Here, in the case of a symmetrical structure, the outer layers can be selected so that they have the best possible properties for discharge of the coextrudate at the slit die and that the inner layer(s) has/have the desired mechanical and/or thermal properties.
Both in this case and especially in the case of an unsymmetrical structure, the outer layer facing away from the aluminum foil (later located on the container side) can also take account of the nature of the material of the cup/container on to the rim of which the lid is sealed. In this case, this may be a layer of Appeel 20D745 from DuPont, optionally with from 2 to 5%
of lubricant additive such as Conpol 20S2 from DuPont, in order to seal both against PS cups and against PP
cups.
,
- 10 -In the case of a symmetrical structure (in which the weights per unit area of corresponding layers can, however, be different), for example: PG7004 (unfilled PE)//007209 (filled PE)//PG7004, the stiffness and elasticity of the total film can be influenced in a targeted way. Another combination which has been found to be useful in experiments is: PG7004//Appeel 20D745 (unfilled EMA) or Appeel 20D855 (EMA with filler), both from DuPont//PG7004. Instead of EMA, it is also possible to use other ionomers, e.g. Surlyn 1652-E.
Further compositions which can be used in practice are:
Based on PE: three-layer system, 70 pm:
14 g//CC7209 49 g//PG7004 7g.
Based on PP: Hifax DKS 208 nat 16 g//WG3500 28 g//Hifax DKS208 nat 6 g; here, 22 g//40 g//8 g also give good results.
A particularly suitable combination of constituents for the lid according to the invention has, in the sealed-on state from the outside inward, an aluminum layer, a layer of "bonding agent" and then at least one layer referred to hereinafter as "functional layer". As can be seen from this cursory listing, all layers customary for printing and also others are not mentioned; only the layers which are located on both sides of the contact surface at which separation occurs, and therefore also referred to as separation plane, are listed in the presentation of this combination.
The difficulties of proper separation of the layers which can be seen from the prior art cited at the outset can, according to this aspect of the invention, be eliminated by providing a layer of a "bonding agent"
which forms a particularly intimate bond with the aluminum and thus forms a layer which adheres strongly thereto on the side facing the separation plane. The
Further compositions which can be used in practice are:
Based on PE: three-layer system, 70 pm:
14 g//CC7209 49 g//PG7004 7g.
Based on PP: Hifax DKS 208 nat 16 g//WG3500 28 g//Hifax DKS208 nat 6 g; here, 22 g//40 g//8 g also give good results.
A particularly suitable combination of constituents for the lid according to the invention has, in the sealed-on state from the outside inward, an aluminum layer, a layer of "bonding agent" and then at least one layer referred to hereinafter as "functional layer". As can be seen from this cursory listing, all layers customary for printing and also others are not mentioned; only the layers which are located on both sides of the contact surface at which separation occurs, and therefore also referred to as separation plane, are listed in the presentation of this combination.
The difficulties of proper separation of the layers which can be seen from the prior art cited at the outset can, according to this aspect of the invention, be eliminated by providing a layer of a "bonding agent"
which forms a particularly intimate bond with the aluminum and thus forms a layer which adheres strongly thereto on the side facing the separation plane. The
- 11 -adjoining functional layer and optionally a further layer known as the second layer is Selected so that it seals as strongly as possible against the cup or container in question, which usually comprises a PP
material. It follows therefrom that the adhesion between the "bonding agent" and the functional layer which is in contact therewith has to be less than the adhesion between aluminum and "bonding agent" and also the adhesion between functional layer and cup in the region of the seal. When at least one second layer is provided in addition to the functional layer, this condition also applies to the adhesion in any of the contact surfaces formed between these.
According to some embodiments, these conditions are satisfied when using a "bonding agent" based on ethylene-acrylic acid copolymers, EAA for short, in an excellent way. Here, not only the excellent adhesion of EAA in all its concentration ranges to aluminum in the form of all alloys and embodiments customary for lids (with the adhesion increasing with increasing proportion of acrylic acid) but also the fact that EAA
builds up good adhesion to polyethylene and that this adhesion can be increased by increasing the proportion of ethylene in the EAA and, conversely, can be reduced by increasing the proportion of acrylic acid are particularly advantageous. This makes it possible, given a knowledge of the material of the cup and the quality of the closure to be produced and also of the aluminum used and the other boundary conditions, to establish, by means of a few experiments, the composition of the EAA at which the desired adhesion and separation properties are achieved for the lid.
A further particular property of EAA which may be noted is that it has poor adhesion to polypropylene, so that it is possible to influence further the desired adhesion values by means of an appropriate composition
material. It follows therefrom that the adhesion between the "bonding agent" and the functional layer which is in contact therewith has to be less than the adhesion between aluminum and "bonding agent" and also the adhesion between functional layer and cup in the region of the seal. When at least one second layer is provided in addition to the functional layer, this condition also applies to the adhesion in any of the contact surfaces formed between these.
According to some embodiments, these conditions are satisfied when using a "bonding agent" based on ethylene-acrylic acid copolymers, EAA for short, in an excellent way. Here, not only the excellent adhesion of EAA in all its concentration ranges to aluminum in the form of all alloys and embodiments customary for lids (with the adhesion increasing with increasing proportion of acrylic acid) but also the fact that EAA
builds up good adhesion to polyethylene and that this adhesion can be increased by increasing the proportion of ethylene in the EAA and, conversely, can be reduced by increasing the proportion of acrylic acid are particularly advantageous. This makes it possible, given a knowledge of the material of the cup and the quality of the closure to be produced and also of the aluminum used and the other boundary conditions, to establish, by means of a few experiments, the composition of the EAA at which the desired adhesion and separation properties are achieved for the lid.
A further particular property of EAA which may be noted is that it has poor adhesion to polypropylene, so that it is possible to influence further the desired adhesion values by means of an appropriate composition
- 12 -of the functional layer which comes into contact with the EAA. When more than 50% of polypropylene polymers (homopolymer, copolymer and/or TPO = thermoplastic olefin) is present and a particular proportion of polyethylene which can be established by means of a few experiments, preferably below 25%, is present, the necessary minimum adhesion at the separation plane can be achieved using an EEA containing about 9% of acrylic acid without the adhesion being so strong that peeling-off would be problematical.
At a higher proportion of acrylic acid, for example 12%
and above, it is also possible to use a functional layer having a PE content of 40% and above without destroying the desired peeling effect; this system composed of "bonding agent" and functional layer can be employed usefully within a wide range by matching to the known boundary conditions in each case by a person skilled in the art.
In addition, it should also be stated that, as in the two abovementioned examples, various fillers such as talc, titanium oxide, chalk and colored pigments which do not appreciably change the adhesion behavior of the layer itself can be used in the functional layer. In particular cases, the PE can be at least partly replaced by ethylene copolymers such as EMA (ethylene-methyl acrylate); the layer can also consist entirely of polypropylene or an 80:20 mixture of PP:EMA.
A further advantage of the use of such a functional layer comprising essentially PE and PP is that the proportion of PE has a favorable effect on the processing behavior of the mixture.
A second layer can adjoin the abovementioned functional layer, particularly when this is desirable in order to achieve specific effects on sealing or when, for any
At a higher proportion of acrylic acid, for example 12%
and above, it is also possible to use a functional layer having a PE content of 40% and above without destroying the desired peeling effect; this system composed of "bonding agent" and functional layer can be employed usefully within a wide range by matching to the known boundary conditions in each case by a person skilled in the art.
In addition, it should also be stated that, as in the two abovementioned examples, various fillers such as talc, titanium oxide, chalk and colored pigments which do not appreciably change the adhesion behavior of the layer itself can be used in the functional layer. In particular cases, the PE can be at least partly replaced by ethylene copolymers such as EMA (ethylene-methyl acrylate); the layer can also consist entirely of polypropylene or an 80:20 mixture of PP:EMA.
A further advantage of the use of such a functional layer comprising essentially PE and PP is that the proportion of PE has a favorable effect on the processing behavior of the mixture.
A second layer can adjoin the abovementioned functional layer, particularly when this is desirable in order to achieve specific effects on sealing or when, for any
- 13 -reason, the material with which the lid comes into contact makes it appear to be advisable. A further reason can be the production of the lid sheet by coextrusion, since the functional layer mentioned tends to form a "die beard", which again and again leads to extrusion malfunctions. The formation of such a die beard involves formation of deposits, in particular of filler, on the lip of the extrusion die; these deposits disrupt the formation of a defect-free surface and become detached after reaching a particular size, which leads to damage to the lid sheet. On the other hand, when a second layer, for example comprising 30% of LDPE
and 70% of PP, is coextruded as outermost layer with the functional layer, the sealability against a PP
container is improved further and, secondly, the formation of the die beard is reliably avoided. Since, in addition, excellent adhesion conditions prevail between the functional layer and the second layer, such an embodiment is preferred.
In various tests, excellent results were achieved using the materials mentioned when the "bonding agent" was applied in an amount of from 7 to 8 g/m2, the functional layer was applied in an amount of about 12 g/m2 and the second layer was applied in an amount of about 5 g/m2. The results make it clear that, in particular, the amount of the "bonding agent" can still be reduced.
Merely as obiter dictum, it should be pointed out that both the functional layer and the second layer can contain fillers, in particular talc, in the amounts customary in the production of lids. Three examples of the composition of the functional layer will make this clear.
and 70% of PP, is coextruded as outermost layer with the functional layer, the sealability against a PP
container is improved further and, secondly, the formation of the die beard is reliably avoided. Since, in addition, excellent adhesion conditions prevail between the functional layer and the second layer, such an embodiment is preferred.
In various tests, excellent results were achieved using the materials mentioned when the "bonding agent" was applied in an amount of from 7 to 8 g/m2, the functional layer was applied in an amount of about 12 g/m2 and the second layer was applied in an amount of about 5 g/m2. The results make it clear that, in particular, the amount of the "bonding agent" can still be reduced.
Merely as obiter dictum, it should be pointed out that both the functional layer and the second layer can contain fillers, in particular talc, in the amounts customary in the production of lids. Three examples of the composition of the functional layer will make this clear.
- 14 -Constituent Example 1 Example 2 Example 3 (% by (% by (% by weight) weight) weight) PP homopolymer* 30 56 40 PP random copolymer 40 0 0 TPO = thermoplastic 0 0 35 polyolefin Talc 10 20 10 * Mixture of various PP grades having different viscosities As laser source, it is possible to use, for example, a StarScribe OW from Carl Baasel Lasertechnik, Starnberg, Germany. This CO2 laser is particularly suitable for scoring film laminates and has a wavelength of 10.6 pm at a power of 300 W, in the case of some models also 360 W and in special cases up to 450 W, in the case of some models also wavelengths of 10.25 pm. The lid material present in the form of a continuous sheet (usually in a width of two lids offset next to one another) is, with the polymer layer facing the laser and sliding on a suitable support coming from a stock roll, moved past the laser and after processing is wound up on a drum. The laser beam is appropriately moved over the surface by means of two or three axially moveable mirrors; the laser source is usually stationary.
The focusing (or the theoretical center thereof) of the beam is preferably on to a point above, preferably just above, the aluminum foil so that the greatest intensity of energy input is deep in the interior of the usually multilayer polymer film (if the term "deep" is appropriate at all at the thicknesses indicated). As a guide, it can be said that focusing, seen from the side of the incidence of the laser, should be at a point
The focusing (or the theoretical center thereof) of the beam is preferably on to a point above, preferably just above, the aluminum foil so that the greatest intensity of energy input is deep in the interior of the usually multilayer polymer film (if the term "deep" is appropriate at all at the thicknesses indicated). As a guide, it can be said that focusing, seen from the side of the incidence of the laser, should be at a point
- 15 -which is located at a depth between 75% and 90%, preferably between 80% and 85%, of the thickness of the layer to be treated with the laser. The layer to be treated with the laser is the layer between the outermost surface of the lid and the surface of the aluminum foil facing the laser. The focusing itself reaches diameters of from 150 pm to 350 pm, with preference being given to regions in the range from 170 pm to 210 pm. In this way, the weakening of the material during movement of the laser is concentrated on only a very narrow region, and excess energy is quickly removed without causing damage by the highly thermally conductive, nearby aluminum foil.
As a simple but reliable rule of thumb, it can be said that the weakening of the polymer film is sufficient but not too great when a linear region having a slightly increased (compared to the surrounding area) reflection can be discerned by the naked eye on the surface of the aluminum foil on close examination after removal of the polymer film. A conspicuous line indicates excessive energy input, while a change which cannot be discerned or can be barely discerned even with increased attention points to insufficient energy input. This classification is not actually quantifiable, but the optical change resists a more objective definition.
The speed of the point of incidence of the laser beam on the surface of the lid material is from a few mm/s to some cm/s, preferably from 5 mm/s to 5 cm/s, depending on the nature and the thickness of the layers to be weakened and the desired degree of weakening.
The cut obtained in the mode of operation described is so narrow that the material cannot, even if it is present in liquid form, penetrate through to the aluminum. The relocation process of the molten but at
As a simple but reliable rule of thumb, it can be said that the weakening of the polymer film is sufficient but not too great when a linear region having a slightly increased (compared to the surrounding area) reflection can be discerned by the naked eye on the surface of the aluminum foil on close examination after removal of the polymer film. A conspicuous line indicates excessive energy input, while a change which cannot be discerned or can be barely discerned even with increased attention points to insufficient energy input. This classification is not actually quantifiable, but the optical change resists a more objective definition.
The speed of the point of incidence of the laser beam on the surface of the lid material is from a few mm/s to some cm/s, preferably from 5 mm/s to 5 cm/s, depending on the nature and the thickness of the layers to be weakened and the desired degree of weakening.
The cut obtained in the mode of operation described is so narrow that the material cannot, even if it is present in liquid form, penetrate through to the aluminum. The relocation process of the molten but at
- 16 -least softened polymer of the disrupted region, which has the shape of an extremely narrow notch, which occurs up to cooling is also refilled at least at the bottom without this leading to restoration of the mechanical strength of the weakened layer.
To keep the foil flat during the movement over the support, the support can be provided with openings which are connected to a suction device and thus suck the foil against the defined surface of the support as a result of the pressure difference. The correct degree of subatmospheric pressure can be determined by a person skilled in the art by means of a few experiments as a function of the foil speed, the foil strength and the quality of the line of weakening obtained.
This combination of materials and the treatment thereof achieves the abovementioned objective even on an industrial scale with sufficient accuracy, reliability and at commercially acceptable cost.
It is assumed that other types of laser are also able to produce appropriate lines of weakening, although the CO2 laser has produced the best results in experiments carried out by the applicant. Progress in the field of laser technology has recently also made the use of CO2 lasers having a power of 100 W with virtually unchanged operating parameters possible; a person skilled in the field of lid production and having knowledge of the invention and the desired lid can use such lasers appropriately after a few experiments.
At least one cohesively closed line of weakness which defines the future drinking opening is in this way applied to each individual lid. In addition, a further, then preferably smaller, opening which serves either for admission of air during drinking or for pushing in
To keep the foil flat during the movement over the support, the support can be provided with openings which are connected to a suction device and thus suck the foil against the defined surface of the support as a result of the pressure difference. The correct degree of subatmospheric pressure can be determined by a person skilled in the art by means of a few experiments as a function of the foil speed, the foil strength and the quality of the line of weakening obtained.
This combination of materials and the treatment thereof achieves the abovementioned objective even on an industrial scale with sufficient accuracy, reliability and at commercially acceptable cost.
It is assumed that other types of laser are also able to produce appropriate lines of weakening, although the CO2 laser has produced the best results in experiments carried out by the applicant. Progress in the field of laser technology has recently also made the use of CO2 lasers having a power of 100 W with virtually unchanged operating parameters possible; a person skilled in the field of lid production and having knowledge of the invention and the desired lid can use such lasers appropriately after a few experiments.
At least one cohesively closed line of weakness which defines the future drinking opening is in this way applied to each individual lid. In addition, a further, then preferably smaller, opening which serves either for admission of air during drinking or for pushing in
- 17 -a drinking straw can be defined by a further line of weakness.
An embodiment which has been found to be useful in practice concerns the formation of the line of weakness in the region of the opening tab in the form of a serpentine line which "winds" around the future sealing seam. This ensures that both the opening of the packaging and also separation of the polymer film from the aluminum foil occur reliably and cleanly. Without this measure, it is possible, particularly in the case of PP-based polymer films for separation of the two layers not to occur or to occur only very unsatisfactorily.
The production of the line of weakness by means of a laser is readily discernible on the finished lid since the abovementioned optical change on the aluminum layer is formed only when the line of weakness is produced by means of a laser. Both purely mechanical and mechanothermal production of the line of weakness result in a completely different form of the line of weakness; in particular this is significantly broader and exposes noticeable regions of the surface of the aluminum foil.
A new field of application for such lids having foils having specifically configured openings remaining on the container rim after peeling-off is medicine bottles in which, despite the name, not liquids but solid pills, tablets, coated tablets, capsules, etc., which usually have no further packaging are present in large numbers. As a result of the configuration according to the invention of the opening in the foil, the large opening can, before sealing by the packager, be used for convenient and rapid filling and the user is provided with an appropriately small opening which aids individual rolling-out of the pellet-like contents.
An embodiment which has been found to be useful in practice concerns the formation of the line of weakness in the region of the opening tab in the form of a serpentine line which "winds" around the future sealing seam. This ensures that both the opening of the packaging and also separation of the polymer film from the aluminum foil occur reliably and cleanly. Without this measure, it is possible, particularly in the case of PP-based polymer films for separation of the two layers not to occur or to occur only very unsatisfactorily.
The production of the line of weakness by means of a laser is readily discernible on the finished lid since the abovementioned optical change on the aluminum layer is formed only when the line of weakness is produced by means of a laser. Both purely mechanical and mechanothermal production of the line of weakness result in a completely different form of the line of weakness; in particular this is significantly broader and exposes noticeable regions of the surface of the aluminum foil.
A new field of application for such lids having foils having specifically configured openings remaining on the container rim after peeling-off is medicine bottles in which, despite the name, not liquids but solid pills, tablets, coated tablets, capsules, etc., which usually have no further packaging are present in large numbers. As a result of the configuration according to the invention of the opening in the foil, the large opening can, before sealing by the packager, be used for convenient and rapid filling and the user is provided with an appropriately small opening which aids individual rolling-out of the pellet-like contents.
- 18 -Instead of medicines, this can also be used for confectionery, chewing gum in appropriate form, lozenges, pastilles, etc.
The invention is not restricted to the examples described but can be modified in a variety of ways.
Thus, it is possible to use, in particular, polymers or polymer mixtures different from those indicated, even when the fundamentals, viz. the PE- or PP-based polymer films, remain.
In the abovementioned embodiment of the invention, these objectives, viz, avoidance of the problem of excessively strong sealing, are achieved by, in a lid of the type mentioned at the outset, the cohesively closed line of weakness being arranged as close as possible to the sealing rim on its inside, sometimes also in the interior region of the sealing rim, regardless of the way in which the line of weakness is produced, even though it is preferably produced by a laser here.
In this way, the seal is not peeled off on pulling off the lid, but instead the composite of the aluminum foil and the polymer film in this region, with the polymer film remaining on the lid over virtually the entire opening of the cup and thus making free the entire opening.
In a preferred embodiment, the line of weakness is located in a region relative to the sealing rim which on its interior contour is delimited by a line which has a spacing from the inner edge of the sealing rim corresponding to the width of the sealing rim and whose outer contour runs within the sealing rim, with the spacing from the inner edge of the sealing rim being not more than one third, preferably not more than one
The invention is not restricted to the examples described but can be modified in a variety of ways.
Thus, it is possible to use, in particular, polymers or polymer mixtures different from those indicated, even when the fundamentals, viz. the PE- or PP-based polymer films, remain.
In the abovementioned embodiment of the invention, these objectives, viz, avoidance of the problem of excessively strong sealing, are achieved by, in a lid of the type mentioned at the outset, the cohesively closed line of weakness being arranged as close as possible to the sealing rim on its inside, sometimes also in the interior region of the sealing rim, regardless of the way in which the line of weakness is produced, even though it is preferably produced by a laser here.
In this way, the seal is not peeled off on pulling off the lid, but instead the composite of the aluminum foil and the polymer film in this region, with the polymer film remaining on the lid over virtually the entire opening of the cup and thus making free the entire opening.
In a preferred embodiment, the line of weakness is located in a region relative to the sealing rim which on its interior contour is delimited by a line which has a spacing from the inner edge of the sealing rim corresponding to the width of the sealing rim and whose outer contour runs within the sealing rim, with the spacing from the inner edge of the sealing rim being not more than one third, preferably not more than one
- 19 -quarter, of the width of the sealing rim. These measures ensure, even in the case of relatively large tolerances in respect of the position of the sealing rim, that, firstly, the line of weakness coincides very precisely with the inner rim of the cup or the cup opening and, secondly, the line of weakness is not so deep in the sealing rim that peeling off of the aluminum foil from the polymer film occurs from there, which would leave the polymer film on the rim of the cup.
Non-limiting examples of embodiments of the invention will be illustrated below with the aid of the drawings. Here, fig. 1 shows the upper rim region of a partly opened cup, fig. 2 shows a bottom view of a lid and fig. 3 shows a detail.
Fig. 1 shows a perspective, schematic view of the upper region of a cup 1 which is/was closed by a lid 2 according to an embodiment the invention which is partly peeled off. At the sealing rim 10 of the cup 1, an annular part 21 of the lid 2, comprising the aluminum layer and the laminated-on polymer film, has remained; separation occurs along the line of weakness 3. The broken line 11 indicates the inner contour of the sealing rim in order to show the closeness of this inner contour 11 of the sealing rim to the line of weakness 3.
The peeled-off part of the lid 2 has the aluminum layer and the laminated-on polymer film in its central region 22, and only the aluminum layer in its rim region 23 since the polymer film remains on the sealing rim 10 in this region.
It can be seen from fig. 2 that in the region of the tab 16 it is possible to provide an outer line of weakness 17, optionally having a wavy shape, in order . :
Non-limiting examples of embodiments of the invention will be illustrated below with the aid of the drawings. Here, fig. 1 shows the upper rim region of a partly opened cup, fig. 2 shows a bottom view of a lid and fig. 3 shows a detail.
Fig. 1 shows a perspective, schematic view of the upper region of a cup 1 which is/was closed by a lid 2 according to an embodiment the invention which is partly peeled off. At the sealing rim 10 of the cup 1, an annular part 21 of the lid 2, comprising the aluminum layer and the laminated-on polymer film, has remained; separation occurs along the line of weakness 3. The broken line 11 indicates the inner contour of the sealing rim in order to show the closeness of this inner contour 11 of the sealing rim to the line of weakness 3.
The peeled-off part of the lid 2 has the aluminum layer and the laminated-on polymer film in its central region 22, and only the aluminum layer in its rim region 23 since the polymer film remains on the sealing rim 10 in this region.
It can be seen from fig. 2 that in the region of the tab 16 it is possible to provide an outer line of weakness 17, optionally having a wavy shape, in order . :
- 20 -to aid separation of the annular part 21 remaining on the sealing rim without leading to damage to the aluminum foil.
Finally, fig. 3 depicts a sealing rim 10, purely schematically with its inner edge 11 and its outer edge 12 and its surroundings. It should be pointed out again that the precise position of the sealing rim 10 both on the rim of the cup and on the lid is determined only on sealing of the cup by the setting of the sealing machine and the tolerances which occur when laying the lid on the rim of the cup; the figure thus starts out, for illustrative purposes, from a previously sealed lid.
With this proviso, the line of weakness (not shown) should be in a region relative to the sealing rim or to the sealing seam indicated by two lines 13, 14: the inner delimiting line 13 is at a distance of not more than 2b, preferably not more than b, from the inner contour 11 of the sealing rim, with b being the width of the sealing rim. The outer delimiting line 14 is in turn at a distance d from the inner contour 11 of the sealing rim 10 which does not exceed a maximum of one third, but preferably a maximum of one quarter, of the width b of the sealing rim 10: d b/3 or preferably:
d __ b/4.
A person skilled in the field of lid production and knowing the tolerances of the apparatuses used can then easily determine the best possible position of the line of weakness on the lid 2, whose outer rim is denoted by 15 and from which the constructor has proceeded. The position of the outer rim of the cup 1 is, for reasons of clarity, not shown in any of the figures.
To be able to check fulfillment of the characteristics according to the invention even in the case of lids . CA 02729044 2010-12-22
Finally, fig. 3 depicts a sealing rim 10, purely schematically with its inner edge 11 and its outer edge 12 and its surroundings. It should be pointed out again that the precise position of the sealing rim 10 both on the rim of the cup and on the lid is determined only on sealing of the cup by the setting of the sealing machine and the tolerances which occur when laying the lid on the rim of the cup; the figure thus starts out, for illustrative purposes, from a previously sealed lid.
With this proviso, the line of weakness (not shown) should be in a region relative to the sealing rim or to the sealing seam indicated by two lines 13, 14: the inner delimiting line 13 is at a distance of not more than 2b, preferably not more than b, from the inner contour 11 of the sealing rim, with b being the width of the sealing rim. The outer delimiting line 14 is in turn at a distance d from the inner contour 11 of the sealing rim 10 which does not exceed a maximum of one third, but preferably a maximum of one quarter, of the width b of the sealing rim 10: d b/3 or preferably:
d __ b/4.
A person skilled in the field of lid production and knowing the tolerances of the apparatuses used can then easily determine the best possible position of the line of weakness on the lid 2, whose outer rim is denoted by 15 and from which the constructor has proceeded. The position of the outer rim of the cup 1 is, for reasons of clarity, not shown in any of the figures.
To be able to check fulfillment of the characteristics according to the invention even in the case of lids . CA 02729044 2010-12-22
- 21 -which have not yet been sealed, it should be stated that the line of weakness encloses at least 70%, preferably at least 75% or better 85%, of the surface area of the lid, without taking into account any tab present; the greater the area of the lid, the larger the enclosed proportion. This corresponds in the case of a circular lid having an external diameter of 75 mm (and disregarding the tab) to a diameter of the likewise circular line of weakness of (about) 68 mm or of (about) 70 mm, disregarding any serpentine lines or other configurations.
At an external diameter of 95 mm of the lid, the invention provides for a diameter of the line of weakness of from 81 to 85 mm, depending on the configuration of the sealing rim, which corresponds to an enclosed proportion of the area of from 72% to 80%.
At an external diameter of 95 mm of the lid, the invention provides for a diameter of the line of weakness of from 81 to 85 mm, depending on the configuration of the sealing rim, which corresponds to an enclosed proportion of the area of from 72% to 80%.
Claims (57)
1. A lid for closing a cup along a circumferential sealing rim, the lid comprising at least an aluminum foil and a plastics material film coextruded onto the aluminum foil, a cohesive line of weakness being provided in the plastics material film, at least one layer of the plastics material film comprising either polyethylene (PE)-based plastics material or polypropylene (PP)-based plastics material, wherein the aluminum layer is adjoined by a layer based on ethylene-acrylic acid copolymers and at least one functional layer attached thereto, which contains mainly polyethylene and polypropylene polymers.
2. A lid according to claim 1, wherein the functional layer contains at least 50 % by weight of polypropylene polymers.
3. A lid according to claim 2, wherein the polypropylene polymers comprise one or more of homopolymers, copolymers and thermoplastic olefins (TPO).
4. A lid according to claim 1, 2 or 3, wherein the functional layer contains at most 25 % by weight of polyethylene polymers.
5. A lid according to any one of claims 1 to 4, further comprising, attached to the functional layer, a second layer which contains mainly polyethylene and polypropylene polymers having a higher proportion of polypropylene than the functional layer.
6. A lid according to any one of claims 1 to 5, connected to a cup by means of a circumferential sealing rim, wherein the cohesive line of weakness is provided in a region relative to the circumferential sealing rim which is delimited by two lines, the inner line inside the inner contour of the scaling rim is at a distance from the inner contour of at most twice the width of the sealing rim, and the outer line outside the inner contour of the sealing rim is at a distance from the inner contour of at most one third of the width of the sealing rim.
7. A lid according to claim 6, wherein the distance of the inner line from the inner contour is smaller than the width of the sealing rim.
8. A lid according to claim 6, wherein the distance of the outer line from the inner contour is smaller than one quarter of the width of the sealing rim.
9. A lid according to any one of claims 1 to 8, comprising a tab for opening, and wherein in the region thereof a line of weakness having a serpentine shape is provided in the sealing seam.
10. A lid according to any one of claims 1 to 9, wherein the cohesive line of weakness encloses at least 70 % of the surface of the lid, without taking into consideration the possible presence of a tab.
11. A lid according to any one of claims 1 to 9, wherein the cohesive line of weakness encloses at least 75 % of the surface of the lid, without taking into consideration the possible presence of a tab.
12. A lid according to any one of claims 1 to 9, wherein the cohesive line of weakness encloses at least 85 % of the surface of the lid, without taking into consideration the possible presence of a tab.
13. A lid according to any one of claims 1 to 12, wherein said plastics material film comprises a multilayer plastics material film.
14. A lid according to any one of claims 1 to 13, wherein the line of weakness is introduced into the plastics material film by means of a CO2 laser.
15. A lid according to any one of claims 1 to 14, comprising a layer of hot sealing varnish between the aluminum foil and the coextruded plastics material film.
16. A lid according to claim 15, wherein the layer of hot sealing varnish is one of or both PVC free and colourless.
17. A lid as claimed in any one of claims 1 to 16 having a polymer film based on PE that comprises a three-layer system having a thickness of about 70 µm, where the layer facing the cup interior is PG7004 in an amount of 14 g/m2, the middle layer is CC7209 in an amount of 49 g/m2 and the layer facing the aluminum is PG7004 in an amount of 7 g/m2.
18. The lid as claimed in any one of claims 1 to 14 having a polymer film based on PP that comprises a three-layer system having a thickness of about 70 µm, where the layer facing the cup interior is Hifax DKS 208 nat in an amount of 16 g/m2, the middle layer is WG350C in an amount of 28 g/m2 and the layer facing the aluminum is Hifax DKS208 nat in an amount of 6 g/m2.
19. A lid for closing a cup along a circumferential sealing rim, the lid comprising:
an aluminum foil; and a functional layer coextruded onto the aluminum foil;
wherein the functional layer comprises one or more layers of a polymer film that is based upon polyethylene (PE), polypropylene (PP), or a mixture thereof; the polymer film including a cohesive line of weakness introduced by means of a CO2 laser;
wherein the aluminum foil is adjoined to the polymer film by a bonding agent that includes ethylene-acrylic acid copolymers.
an aluminum foil; and a functional layer coextruded onto the aluminum foil;
wherein the functional layer comprises one or more layers of a polymer film that is based upon polyethylene (PE), polypropylene (PP), or a mixture thereof; the polymer film including a cohesive line of weakness introduced by means of a CO2 laser;
wherein the aluminum foil is adjoined to the polymer film by a bonding agent that includes ethylene-acrylic acid copolymers.
20. The lid as claimed in claim 19, wherein the functional layer includes at least 50% polypropylene polymers by weight.
21. The lid as claimed in claim 19, wherein the functional layer contains not more than 25% polyethylene polymers by weight.
22. The lid as claimed in any one of claims 19 to 21, wherein the functional layer further comprises an additional polymer film layer containing polyethylene and polypropylene polymers and having a higher proportion of polypropylene than the first polymer film layer.
23. The lid as claimed in any one of claims 19 to 22, wherein the cohesive line of weakness is provided in a region adjacent to the circumferential sealing rim, the region being bounded by an inner line that is disposed not more than twice the width of the sealing rim from an inner contour of the sealing rim in an inward direction, and an outer line that is disposed a maximum of one-third of the width of the sealing rim outside an inner contour of the sealing rim.
24. The lid as claimed in claim 23, wherein the spacing of the inner line from the inner contour is smaller than the width of the circumferential sealing rim.
25. The lid as claimed in claim 23, wherein the spacing of the outer line from the inner contour of the sealing rim is smaller than one-quarter of the width of the sealing rim.
26. The lid as claimed in claim 23, further comprising a tab for opening the lid, wherein the cohesive line of weakness has a serpentine shape in a region near the tab.
27. The lid as claimed in any one of claims 19 to 26, further comprising a layer of hot sealing varnish disposed between the aluminum foil and the coextruded functional layer.
28. The lid as claimed in claim 27, wherein the hot sealing varnish is PVC-free.
29. The lid as claimed in claim 27 or 28, wherein the hot sealing varnish is colorless.
30. The lid as claimed in any one of claims 19 to 29, wherein the functional layer has a thickness of about 70 pm and includes three layers of polymer film based on polyethylene, wherein the layer facing the cup interior includes an unfilled polyethylene polymer formulation in an amount of 14 g/m2, the middle layer includes a polyethylene polymer formulation including talc filler in an amount of 49 g/m2, and the layer facing the aluminum foil includes the unfilled polyethylene polymer formulation in an amount of 7 g/m2.
31. The lid as claimed in any one of claims 19 to 29, wherein the functional layer has a thickness of about 70 µm and includes three layers of polymer film based on polypropylene, wherein the layer facing the cup interior includes an unfilled polypropylene polymer formulation in an amount of 16 g/m2, the middle layer includes a filled polypropylene polymer formulation in an amount of 28 g/m2 and the layer facing the aluminum foil includes the unfilled polypropylene polymer formulation in an amount of 6 g/m2.
32. A sealed cup, wherein the cup has a circumferential sealing rim and a lid forming a seal along the circumferential sealing rim, the lid comprising:
an outer aluminum foil layer; and a functional layer coextruded onto the aluminum foil layer; wherein the functional layer has a thickness of about 70 µm and includes three layers of polymer film based on polyethylene, wherein the layer facing the cup interior includes an unfilled polyethylene polymer formulation in an amount of 14 g/m2, the middle layer includes a polyethylene polymer formulation including talc filler in an amount of 49 g/m2, and the layer facing the aluminum foil includes the unfilled polyethylene polymer formulation in an amount of 7 g/m2;
wherein the functional layer is joined to the aluminum foil layer by a bonding agent that includes ethylene-acrylic acid copolymers; and the functional layer includes a cohesive line of weakness in one or more constituent polymer films introduced by means of a CO2 laser, the cohesive line of weakness disposed in a region of the functional layer adjacent to the circumferential sealing rim, the region being bounded by an inner line that is disposed not more than twice the width of the sealing rim from an inner contour of the sealing rim in an inward direction, and an outer line that is disposed a maximum of one-third of the width of the sealing rim outside an inner contour of the sealing rim.
an outer aluminum foil layer; and a functional layer coextruded onto the aluminum foil layer; wherein the functional layer has a thickness of about 70 µm and includes three layers of polymer film based on polyethylene, wherein the layer facing the cup interior includes an unfilled polyethylene polymer formulation in an amount of 14 g/m2, the middle layer includes a polyethylene polymer formulation including talc filler in an amount of 49 g/m2, and the layer facing the aluminum foil includes the unfilled polyethylene polymer formulation in an amount of 7 g/m2;
wherein the functional layer is joined to the aluminum foil layer by a bonding agent that includes ethylene-acrylic acid copolymers; and the functional layer includes a cohesive line of weakness in one or more constituent polymer films introduced by means of a CO2 laser, the cohesive line of weakness disposed in a region of the functional layer adjacent to the circumferential sealing rim, the region being bounded by an inner line that is disposed not more than twice the width of the sealing rim from an inner contour of the sealing rim in an inward direction, and an outer line that is disposed a maximum of one-third of the width of the sealing rim outside an inner contour of the sealing rim.
33. A sealed cup, wherein the cup has a circumferential sealing rim and a lid forming a seal along the circumferential sealing rim, the lid comprising:
an outer aluminum foil layer; and a functional layer coextruded onto the aluminum foil layer; wherein the functional layer has a thickness of about 70 µm and includes three layers of polymer film based on polypropylene, wherein the layer facing the cup interior includes an unfilled polypropylene polymer formulation in an amount of 16 g/m2, the middle layer includes a filled polypropylene polymer formulation in an amount of 28 g/m2 and the layer facing the aluminum foil includes the unfilled polypropylene polymer formulation in an amount of 6 g/m2;
wherein the functional layer is joined to the aluminum foil layer by a bonding agent that includes ethylene-acrylic acid copolymers; and the functional layer includes a cohesive line of weakness in one or more constituent polymer films introduced by means of a CO2 laser, the cohesive line of weakness disposed in a region of the functional layer adjacent to the circumferential sealing rim, the region being bounded by an inner line that is disposed not more than twice the width of the sealing rim from an inner contour of the sealing rim in an inward direction, and an outer line that is disposed a maximum of one-third of the width of the sealing rim outside an inner contour of the sealing rim.
an outer aluminum foil layer; and a functional layer coextruded onto the aluminum foil layer; wherein the functional layer has a thickness of about 70 µm and includes three layers of polymer film based on polypropylene, wherein the layer facing the cup interior includes an unfilled polypropylene polymer formulation in an amount of 16 g/m2, the middle layer includes a filled polypropylene polymer formulation in an amount of 28 g/m2 and the layer facing the aluminum foil includes the unfilled polypropylene polymer formulation in an amount of 6 g/m2;
wherein the functional layer is joined to the aluminum foil layer by a bonding agent that includes ethylene-acrylic acid copolymers; and the functional layer includes a cohesive line of weakness in one or more constituent polymer films introduced by means of a CO2 laser, the cohesive line of weakness disposed in a region of the functional layer adjacent to the circumferential sealing rim, the region being bounded by an inner line that is disposed not more than twice the width of the sealing rim from an inner contour of the sealing rim in an inward direction, and an outer line that is disposed a maximum of one-third of the width of the sealing rim outside an inner contour of the sealing rim.
34. A process for producing a lid for closing a cup along a circumferential sealing rim, where the lid comprises at least one aluminum foil and a polymer film coextruded on to the aluminum foil and a cohesive line of weakness is provided in the polymer film, where at least one layer of the polymer film comprises either polymer based on polyethylene (PE) or polymer based on polypropylene (PP) and where the line of weakness has been introduced into the polymer film by means of a laser, wherein lid material in the form of a continuous sheet is conveyed, with the polymer film facing the laser and sliding on an appropriate support, past the laser and the laser beam is focused to a diameter of from 150 µm to 350 µm, and the beam is focused on to a point above the aluminum foil.
35. The process as claimed in claim 34, wherein the laser beam is focused to a diameter of about 210 µm.
36. The process as claimed in claim 34 or 35, wherein the focal point is at a depth in the range from 75% to 90% of the thickness of the layer to be treated by the laser, viewed from the side of incidence of the laser.
37. The process as claimed in claim 36, wherein the focal point is at a depth in the range from 80% to 85% of the thickness of the layer to be treated by the laser.
38. The process as claimed in any one of claims 34 to 37, wherein the wavelength of the laser is in the range from 10.2 µm to 10.8 µm.
39. The process as claimed in any one of claims 34 to 38, wherein the laser beam has an energy of from 100 W to 450 W.
40. The process as claimed in any one of claims 34 to 38, wherein the laser beam has an energy of about 300 W.
41. The process as claimed in any one of claims 34 to 40, wherein the speed of the point of incidence of the laser beam across the surface of the lid material is in the range from mm/s to 50 mm/s, depending on the nature and thickness of the layers to be weakened and the desired degree of weakening.
42. The process as claimed in any one of claims 34 to 41, wherein the polymer film comprises a multilayer polymer film.
43. A medicine bottle which is closed by a lid along a circumferential sealing rim, where the lid comprises at least one aluminum foil and a polymer film coextruded on to the aluminum foil and a cohesive line of weakness is provided in the polymer film, wherein at least one layer of the polymer film comprises either polymer based on polyethylene (PE) or polymer based on polypropylene (PP) and the line of weakness has been introduced into the polymer film by means of a CO2 laser.
44. The medicine bottle as claimed in claim 43, wherein in the lid the aluminum layer is adjoined by a layer based on ethylene-acrylic acid copolymers and adjoining this at least one functional layer comprising essentially polyethylene and polypropylene polymers.
45. The medicine bottle as claimed in claim 44, wherein the functional layer of the lid contains at least 50% of polypropylene polymers.
46. The medicine bottle as claimed in claim 45, wherein the polypropylene polymers comprise one or more of homopolymers, copolymers and thermoplastic olefins (TPO).
47. The medicine bottle as claimed in any one of claims 44 to 46, wherein the functional layer of the lid contains not more than 25% of polyethylene polymers.
48. The medicine bottle as claimed in any one of claims 44 to 47, wherein the lid has, adjoining the functional layer, a second layer containing the essentially polyethylene and polypropylene polymers with a higher proportion of polypropylene than the functional layer.
49. The medicine bottle as claimed in any one of claims 43 to 48, wherein in the lid the cohesive line of weakness is provided in a region relative to the circumferential sealing rim which is bounded by two lines of which the inner line is at a distance of not more than twice the width of the sealing rim from the inner contour of the sealing rim in an inward direction and the outer line is a maximum of one third of the width of the sealing rim outside the inner contour of the sealing rim.
50. The medicine bottle as claimed in claim 49, wherein in the lid, the spacing of the inner line from the inner contour is smaller than the width of the sealing rim.
51. The medicine bottle as claimed in claim 49, wherein in the lid, the spacing of the outer line from the inner contour is smaller than one quarter of the width of the sealing rim.
52. The medicine bottle as claimed in any one of claims 43 to 51, wherein the lid has a tab for opening and in the region thereof a line of weakness having a serpentine shape is provided around the sealing seam.
53. The medicine bottle as claimed in claim 43, wherein the lid has a layer of hot sealing varnish between the aluminum foil and the coextruded polymer film.
54. The medicine bottle as claimed in claim 52, wherein the layer of hot sealing varnish is one of or both PVC free and colourless.
55. The medicine bottle as claimed in any one of claims 43 to 54 having a polymer film based on PE, wherein the lid is a three-layer system having a thickness of about 70 µm, where the layer facing the medicine bottle interior is PG7004 in an amount of 14 g/m2, the middle layer is CC7209 in an amount of 49 g/m2 and the layer facing the aluminum is 9G7004 in an amount of 7 g/m2.
56. The medicine bottle as claimed in any one of claims 43 to 52 having a PP-based polymer film of its lid, wherein the lid is a three-layer system having a thickness of about 70 µm, where the layer facing the medicine bottle interior is Hifax DKS 208 nat in an amount of 16 g/m2, the middle layer is WG350C in an amount of 28 g/m2 and the layer facing the aluminum is Hifax DKS208 nat in an amount of 6 g/m2.
57. The medicine bottle as claimed in any one of claims 43 to 52, wherein said polymer film comprises a multilayer polymer film.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08450095.8 | 2008-06-27 | ||
EP20080450095 EP2138422A1 (en) | 2008-06-27 | 2008-06-27 | Board for sealing a container |
EP09450063.4 | 2009-03-24 | ||
EP20090450063 EP2138421A1 (en) | 2008-06-27 | 2009-03-24 | Board for sealing a container |
PCT/AT2009/000257 WO2009155630A2 (en) | 2008-06-27 | 2009-06-26 | Lid for closing a cup |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2729044A1 CA2729044A1 (en) | 2009-12-30 |
CA2729044C true CA2729044C (en) | 2015-12-22 |
Family
ID=39865728
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA2729044A Expired - Fee Related CA2729044C (en) | 2008-06-27 | 2009-06-26 | Lid for closing a cup |
Country Status (8)
Country | Link |
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US (3) | US8652644B2 (en) |
EP (5) | EP2138422A1 (en) |
BR (4) | BRPI0914299A2 (en) |
CA (1) | CA2729044C (en) |
DK (3) | DK2327635T3 (en) |
MX (1) | MX2010014238A (en) |
PL (3) | PL2327635T3 (en) |
WO (1) | WO2009155630A2 (en) |
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- 2008-06-27 EP EP20080450095 patent/EP2138422A1/en not_active Withdrawn
-
2009
- 2009-03-24 EP EP20090450063 patent/EP2138421A1/en not_active Withdrawn
- 2009-06-26 DK DK11000562T patent/DK2327635T3/en active
- 2009-06-26 DK DK11000560T patent/DK2327636T3/en active
- 2009-06-26 MX MX2010014238A patent/MX2010014238A/en active IP Right Grant
- 2009-06-26 DK DK09768605T patent/DK2321195T3/en active
- 2009-06-26 BR BRPI0914299-1A patent/BRPI0914299A2/en not_active IP Right Cessation
- 2009-06-26 US US13/001,606 patent/US8652644B2/en active Active
- 2009-06-26 EP EP20090768605 patent/EP2321195B1/en not_active Not-in-force
- 2009-06-26 BR BRPI0924483-2A patent/BRPI0924483B1/en not_active IP Right Cessation
- 2009-06-26 PL PL11000562T patent/PL2327635T3/en unknown
- 2009-06-26 CA CA2729044A patent/CA2729044C/en not_active Expired - Fee Related
- 2009-06-26 BR BRPI0924482-4A patent/BRPI0924482B1/en not_active IP Right Cessation
- 2009-06-26 EP EP20110000562 patent/EP2327635B1/en not_active Not-in-force
- 2009-06-26 WO PCT/AT2009/000257 patent/WO2009155630A2/en active Application Filing
- 2009-06-26 PL PL11000560T patent/PL2327636T3/en unknown
- 2009-06-26 BR BRPI0924484A patent/BRPI0924484B1/en active IP Right Grant
- 2009-06-26 EP EP20110000560 patent/EP2327636B1/en not_active Not-in-force
- 2009-06-26 PL PL09768605T patent/PL2321195T3/en unknown
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2010
- 2010-12-27 US US12/979,253 patent/US8905251B2/en not_active Expired - Fee Related
- 2010-12-27 US US12/979,250 patent/US8816248B2/en not_active Expired - Fee Related
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US20110152821A1 (en) | 2011-06-23 |
US20110147353A1 (en) | 2011-06-23 |
EP2327636A1 (en) | 2011-06-01 |
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EP2321195B1 (en) | 2012-12-19 |
BRPI0924483A2 (en) | 2015-08-11 |
BRPI0924483B1 (en) | 2019-05-14 |
BRPI0924482A2 (en) | 2015-08-11 |
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BRPI0924484A2 (en) | 2014-02-04 |
BRPI0924482B1 (en) | 2019-05-28 |
CA2729044A1 (en) | 2009-12-30 |
BRPI0924484B1 (en) | 2019-08-27 |
DK2327635T3 (en) | 2012-11-26 |
EP2327635B1 (en) | 2012-08-22 |
EP2138422A1 (en) | 2009-12-30 |
EP2327636B1 (en) | 2012-08-22 |
WO2009155630A2 (en) | 2009-12-30 |
EP2327635A1 (en) | 2011-06-01 |
DK2321195T3 (en) | 2013-03-18 |
PL2327636T3 (en) | 2013-02-28 |
EP2321195A2 (en) | 2011-05-18 |
BRPI0914299A2 (en) | 2012-12-25 |
PL2327635T3 (en) | 2013-02-28 |
DK2327636T3 (en) | 2012-11-26 |
WO2009155630A3 (en) | 2010-02-25 |
EP2138421A1 (en) | 2009-12-30 |
US8816248B2 (en) | 2014-08-26 |
US8652644B2 (en) | 2014-02-18 |
US8905251B2 (en) | 2014-12-09 |
MX2010014238A (en) | 2011-09-01 |
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